Ageing effect on the mineral and chemical composition of Opalinus Clays (Mont Terri,Switzerland) after excavation and surface storage

Samples of Opalinus Clays from Mont Terri Underground Research Laboratory in the Swiss Jura were analyzed repetitively relative to the duration of their exposure to atmosphere. The objective was the evaluation of such a progressive exposure on the chemical composition of whole-rock samples, and on the chemical and Sr isotopic compositions of leachates obtained by leaching the rock powders with dilute acetic acid. This chemical study was complemented by scanning electron microscope observations to identify the related mineral alterations. The chemical data for the rock powders remained quite constant whatever the duration of the storage, whereas significant changes were observed for the leachates. Similar changes were observed in the leachates of samples collected progressively closer to the walls of a previously excavated niche. When storage time or distance to gallery wall increases, the main variations are: (1) a progressive decrease of the element contents and of the ⁸⁷Sr/⁸⁶Sr ratio in the leachates, (2) an alteration of pyrite followed by precipitation of Ca-sulfate in the rocks, both observed by SEM, and (3) a probable precipitation of new mineral phases in the rocks, such as Fe-oxyhydroxides and/or jarosite that could not be visualized by electron microscopic observation because of their very limited amount and very small grain size. The modifications call for an oxidation of pyrite that probably induced also an oxidation of the organic matter. It could also be shown that the reactions were enhanced by temperature increase, and that they were less pronounced in the samples behind the gallery wall than in the cores stored in laboratory conditions.     

Solute transport in formations of very low permeability: profiles of stable isotope and dissolved noble gas contents of pore water in the Opalinus Clay, Mont Terri, Switzerland

Pore water profiles of water, stable isotope, and dissolved noble gas content have been determined across the Opalinus Clay and adjacent formations at the rock laboratory at Mont Terri. We have found enhanced helium contents (up to [⁴He] = 1 × 10⁻⁴ cubic centimeters at standard pressure and temperature per gram of pore water) and argon isotope ratios (⁴⁰Ar/³⁶Ar ratios up to 334) due to accumulation of ⁴He and ⁴⁰Ar produced in situ. The helium profile was found to be in steady state with respect to in situ production and diffusive loss into the adjacent limestones where groundwater circulates. From this profile a representative mean value of the apparent diffusion coefficient for helium in the pore water of the whole formation was derived for the first time to be D_a = 3.5 × 10⁻¹¹ m² · s⁻¹, which is more than two orders of magnitude lower than the diffusion coefficient D₀ in free water. The stable isotope profile, however, indicates a component of fossil marine pore water, which has not yet been replaced by molecular diffusion of meteoric water from the adjacent limestone and shale formations over the past 10 million years.     

Large-scale tracer profiles in a deep claystone formation (Opalinus Clay at Mont Russelin,Switzerland): Implications for solute transport processes and transport properties of the rock

Natural tracers (Cl^? and stable water isotopes) in pore water of the Opalinus Clay and adjacent formations were studied in the motorway tunnel at Mont Russelin, Switzerland. The Opalinus Clay occurs in the core of an anticline which is cut by a complex system of thrust faults. Concentration profiles of natural tracers were taken from 17 boreholes along a 363 m long section. Pore waters of drillcore samples were analysed with indirect and direct methods. The Cl^? and stable water isotope distribution in the pore water shows a regular and well defined profile, with a conspicuous decrease towards the overlying Dogger limestone aquifer. The highest Cl^? values (approximately 23,000 mg/L) are found in the core of the anticline in Liassic claystones underlying the Opalinus Clay. To quantify the large-scale transport properties of the Opalinus Clay formation, a 2D transport model was constructed and used to reproduce the observed concentration profiles. The calculations indicate that the observed tracer distributions are consistent with diffusion as the dominant transport process. Groundwater flow in the overlying Dogger aquifer was initiated about 2–4 Ma ago, which is long after the folding of the Jura Mountains and probably coincides with the exposure of the aquifer to freshwater recharge following continued erosion of the anticline. The calculations suggest that tracer distributions are controlled by 1) the timing of freshwater recharge in the overlying limestone aquifer, 2) the shape of the anticline and 3) the magnitude and the anisotropy ratio of diffusion coefficients.     

Biogeochemical processes in a clay formation in situ experiment: Part E - Equilibrium controls on chemistry of pore water from the Opalinus Clay, Mont Terri Underground Research Laboratory, Switzerland

The chemistry of pore water (particularly pH and ionic strength) is an important property of clay rocks being considered as host rocks for long-term storage of radioactive waste. Pore waters in clay-rich rocks generally cannot be sampled directly. Instead, their chemistry must be found using laboratory-measured properties of core samples and geochemical modelling. Many such measurements have been made on samples from the Opalinus Clay from the Mont Terri Underground Research Laboratory (URL). Several boreholes in that URL yielded water samples against which pore water models have been calibrated. Following a first synthesis report published in 2003, this paper presents the evolution of the modelling approaches developed within Mont Terri URL scientific programs through the last decade (1997-2009). Models are compared to the composition of waters sampled during dedicated borehole experiments. Reanalysis of the models, parameters and database enabled the principal shortcomings of the previous modelling efforts to be overcome. The inability to model the K concentrations correctly with the measured cation exchange properties was found to be due to the use of an inappropriate selectivity coefficient for Na-K exchange; the inability to reproduce the measured carbonate chemistry and pH of the pore waters using mineral-water reactions alone was corrected by considering clay mineral equilibria. Re-examination of the measured Ca/Mg activity ratios and consideration of the mineralogical composition of the Opalinus Clay suggested that Ca/Mg cation exchange rather than dolomite saturation may control the ratio of these ions in solution. This re-examination also suggests that the Ca/Mg ratio decreases with increasing pore-water salinity. Several possible reasons for this are proposed. Moreover, it is demonstrated that feldspar equilibria must not be included in Opalinus Clay modelling because feldspars are present only in very small quantities in the formation and because Na/K ratios measured in pore water samples are inconsistent with feldspar saturation. The principal need to improve future modelling is additional or better data on rock properties, in particular: (i) a more detailed identification of phases in the Opalinus Clay that include redox-sensitive elements together with evaluation of their thermodynamic properties; (ii) an improved understanding of the distribution of celestite throughout the Opalinus Clay for Sr/SO₄ concentrations control; (iii) improvements in analytic and thermodynamic data for Ca-Mg rock cation exchange and mineral chemical properties and (iv) the measurement of composition and stability constants of clay minerals actually present in the formation.     

Mechanical validation of balanced cross-sections: The case of the Mont Terri anticline at the Jura front (NW Switzerland)

Close to north-west front of the Jura thrust belt in Switzerland, the Mont Terri anticline is located at a disruption of the Muschelkalk decollement, due to a former normal fault. Numerous geological data are available thanks to a motorway tunnel cross-cutting the fold and an underground laboratory. Original field data, two geological maps, a borehole, and a highway tunnel constrain the inner structure. The anticline is characterized by an overturned frontal limb, a steep back limb, and a ramp cross-cutting older normal faults. Three geological cross-sections and three 2D kinematic models are proposed as various combinations of fault-bend folding, fault-propagation folding and detachment folding. The main motivation of this study is to illustrate how geometrical constructions can be constrained by the kinematic approach of limit analysis, which determines the optimal deformation, including faults, that verifies mechanical equilibrium and the Coulomb criterion. Matching some of the important kinematic steps assumed in each three interpretations to the optimal deformation leads us to define the compatible ranges of values of the frictional parameters. These ranges allow us to assess the likeliness of the important kinematic steps of each kinematic model. The present analysis provides a quantitative link between the assumed evolution of the internal structure, and the concomitant evolutions of the topography and of the frictional parameters.     

Biogeochemical processes in a clay formation in situ experiment: Part A - Overview, experimental design and water data of an experiment in the Opalinus Clay at the Mont Terri Underground Research Laboratory, Switzerland

An in situ test in the Opalinus Clay formation, termed porewater chemistry (PC) experiment, was carried out for a period of 5 years. It was based on the concept of diffusive equilibration whereby a traced water with a composition close to that expected in the formation was continuously circulated and monitored in a packed-off borehole. The main original focus was to obtain reliable data on the pH/pCO₂ conditions of the porewater, but because of unexpected microbiologically-induced redox reactions, the objective was extended to elucidate the biogeochemical processes occurring in the borehole and to understand their impact on pH/pCO₂ and porewater chemistry in the low permeability clay formation.The behaviour of the conservative tracers ²H and Br⁻ could be explained by diffusive dilution in the clay and moreover the results showed that diffusive equilibration between the borehole water and the formation occurred within about 3 year’s time. However, the composition and pH/pCO₂ conditions differed considerably from those of the in situ porewater. Thus, pH was lower and pCO₂ was higher than indicated by complementary laboratory investigations. The noted differences are explained by microbiologically-induced redox reactions occurring in the borehole and in the interfacial wall area which were caused by an organic source released from the equipment material. The degradation of this source was accompanied by sulfate reduction and - to a lesser extent - by methane generation, which induced a high rate of acetogenic reactions corresponding to very high acetate concentrations for the first 600 days. Concomitantly with the anaerobic degradation of an organic source, carbonate dissolution occurred and these processes resulted in high pCO₂ and alkalinities as well as drop in pH. Afterwards, the microbial regime changed and, in parallel to ongoing sulfate reduction, acetate was consumed, leading to a strong decrease in TOC which reached background levels after about 1200 days. In spite of the depletion of this organic perturbation in the circuit water, sulfate reduction and methanogenesis continued to occur at a constant rate leading to near-to-constant concentrations of sulfate and bicarbonate as well as pH/pCO₂ conditions until the end of the experiment. The main sink for sulphur was iron sulfide, which precipitated as FeS (am) and FeS₂.The chemical and isotopic composition was affected by the complex interplay of diffusion, carbon degradation rates, mineral equilibria and dissolution rates, iron sulfide precipitation rates, and clay exchange reactions. The ¹³C signals measured for different carbon species showed significant variations which could only be partly explained. The main cations, such as Na, Ca and Mg remained remarkably constant during the experiment, thus indicating the strong buffering of the formation via cation and proton exchange as well as carbonate dissolution/precipitation reactions.     

Drained triaxial testing of shales: insight from the Opalinus Clay

Acta Geotechnica - The investigation of the mechanical behaviour of swelling claystones and shales is challenging because of their very low permeability and of their high sensitivity to changes in...     

Hydrogeology of a fractured shale (Opalinus Clay): Implications for deep geological disposal of radioactive wastes

As part of the Swiss programme for high-level radioactive-waste disposal, a Jurassic shale (Opalinus Clay) is being investigated as a potential host rock. Observations in clay pits and the results of a German research programme focusing on hazardous waste disposal have demonstrated that, at depths of 10–30 m, the permeability of the Opalinus Clay decreases by several orders of magnitude. Hydraulic tests in deeper boreholes (test intervals below 300 m) yielded hydraulic conductivities <10^–12 m/s, even though joints and faults were included in some of the test intervals. These measurements are consistent with hydrogeological data from Opalinus Clay sections in ten tunnels in the Folded Jura of northern Switzerland. Despite extensive faulting, only a few indications of minor water inflow were encountered in more than 6,600 m of tunnel. All inflows were in tunnel sections where the overburden is less than 200 m. The hydraulic data are consistent with clay pore-water hydrochemical and isotopic data. The extensive hydrogeological data base – part of which derives from particularly unfavourable geological environments – provides arguments that advective transport through faults and joints is not a critical issue for the suitability of Opalinus Clay as a host rock for deep geological waste disposal. Electronic Publication     

Influence of water-extractable organic matter from Opalinus Clay on the sorption and speciation of Ni(II), Eu(III) and Th(IV)

The influence of water-extractable organic matter from 6 Opalinus Clay (OPA) samples from Mont Terri and Benken (Switzerland) on the sorption of Ni(II), Eu(III) and Th(IV) has been measured using an ion exchange technique. OPA is considered to be one of the potential host rocks for the deep geological disposal of high-level and long-lived intermediate-level radioactive waste in Switzerland. Within the range of estimated uncertainties, no significant differences in sorption were observed in most cases as compared with suitable synthetic waters devoid of organic C. Only in certain individual cases were slight reductions in sorption (less than a factor of 5) for Eu(III) and Ni(II) found. The results of accompanying laser fluorescence spectroscopy experiments did not show any influence of the extracts on Cm(III) speciation. This would suggest that the reduction of sorption occasionally observed in the ion exchange experiments is probably not caused by the formation of complexes between the radionuclides and the organic matter in the extracts, but is rather due to an underestimation of systematic uncertainties. From these findings, and from UV–VIS spectroscopic characterisation of the organic matter in the extracts, it can be concluded that only a negligible fraction of the organic matter present may be in the form of humic or fulvic acids. It is consequently justified to put aside overly conservative assumptions with respect to the complexing behaviour of the organic matter used towards the metal ions investigated and their chemical analogues. In view of the site-specific character of the present study, these conclusions may not be arbitrarily applied to other geological formations considered as possible host rocks for the disposal of radioactive waste.     

A comparative analysis of trace metal pollution parity between sandy and shaly soils: evidence from two mechanic villages in the Imo River basin

Heavy metal enrichment parity in sandy and shaly mechanic village (MV) soils was studied in order to explain the technical and economic imperatives of setting an environmentally friendly MV on either soil. Okigwe (shaly) and Nekede (sandy) mechanic village soils in the Imo River basin Nigeria were tested and compared. Spectroscopic analysis of the soil samples collected from three surface layers (L), where L1: 0–10 cm; L2: 10–20 cm and L3: 90–100 cm shows that Pb > Cu > Mn in the Okigwe MV, and Mn > Pb > Cu in the Nekede MV. Mean concentration of metals (mg kg⁻¹) in Okigwe MV are Fe: 51,291 ± 18,148, Ni: 22 ± 4, Cd: 20 ± 3, Pb: 500 ± 513, Cu: 616 ± 369, Cr: 16 ± 9, and Mn: 378 ± 207. Similarly, Nekede MV has 22,101 ± 7,273 of Fe; 8 ± 0.8 of Ni; 11 ± 4 of Cd; 320 ± 122 of Pb; 265 ± 145 of Cu; 11 ± 2 of Cr; and 350 ± 191 of Mn. Pollution factor (Pf): Okigwe MV has 0.77, and Nekede has 0.68. Pollution degree: Okigwe MV is greater in L1 and L2, while Nekede is greater in L3, with greater potentials for Pb, and Mn mobility than the Okigwe. Both have similar trends of metal distribution, and significant correlation with their background values. Low clay-silt content in Nekede MV soil suggests low sorption capacity, whereas the high clay-silt content (47–64%) of the Okigwe soil suggests lower bioavailability. Infiltration basin is not recommended in a MV on sandy soil if water table is near surface. In such case, the MV must be moved to a location where water table is >37 m, or have clay-shale material transported to the site to form impervious layer base for detention basin. For groundwater safety and sustainability, shaly soils are most recommended for MVs so that detention basin could be economically used for storm water treatment.     

Biomarker transformations as constraints for the depositional environment and for maximum temperatures during burial of Opalinus Clay and Posidonia Shale in northern Switzerland

Samples from two argillaceous formations (Opalinus Clay and Posidonia Shale) of near-identical maturity from northern Switzerland were subjected to a geochemical characterisation of organic matter and to confined-system pyrolysis experiments. Throughout the study area, the characteristics of organic matter are similar, indicating a spatially homogeneous sedimentary facies. Posidonia Shale contains marine organic matter deposited in a reducing environment, while a predominantly terrigenous source and a more oxidising environment of deposition was identified for Opalinus Clay. In the western and central parts of the study area, organic maturity is close to the onset of oil generation. In the easternmost part, a higher maturity has been reached due to a deeper burial below thick Tertiary Molasse deposits.Isothermal pyrolysis experiments were conducted at temperatures between 250 and 390 °C over 24 h. Bitumen yields increase along similar pathways for both Opalinus Clay and Posidonia Shale, but the maximum values are displaced by 10–20 °C. Data pertaining to maturity were determined from GC–MS analyses of saturated hydrocarbons, and specific attention was given to C₂₉-sterane and C₃₂-hopane isomerisation ratios. The evolution of these parameters with rising temperature is slightly different in the two formations, which is attributed to the contrasting organic facies. The pyrolysis data, together with literature data from natural basins, were used to calculate kinetic parameters for C₂₉-sterane and C₃₂-hopane, assuming a single-step isomerisation scheme according to the Arrhenius law. The resulting values based on pyrolysis data alone are very similar to those based on the combination of pyrolysis and natural data. Activation energies are similar in both formations, while the frequency factors are up to one order of magnitude higher for Posidonia Shale when compared to Opalinus Clay. For the Benken site, maximum temperature during Cretaceous burial was calculated on the basis of the kinetic data, using the TTI approach. The resulting temperatures of 75–80 °C are 5–10 °C below those derived in the literature from apatite fission-track analysis, vitrinite reflectance and basin modelling.     

Faults and fractures in the Gallery 04 of the Mont Terri rock laboratory: Characterization,simulation and application

This paper deals with the reconstruction of a fracture network observed in an underground gallery of a tunnel buried in clay stones in Switzerland, below Mont Terri. The trace maps of the Gallery 04 and of the EZ-G niche of this site have first been digitized and used in various ways to characterize the data. The traces have been divided into two groups, i.e., the pre-existing faults in the gallery and the fractures of the excavated damaged zone (EDZ) in the niche. Each group has been analyzed individually. The number of data for the faults has turned out to be statistically significant, while it was very limited for the EDZ fractures. For both cases, the major statistical characteristics of the traces have been extracted and a reconstruction procedure developed and tested. A full example has been worked out; a gallery immersed in a reconstructed fractured porous medium has been meshed, and the electrical field created by a dipole at the wall calculated by solving the three dimensional Laplace equations in the fractures and in the porous medium.     

Ductile-brittle transition in pre-Alpine amphibolite facies mylonites during evolution from water-present to water-deficient conditions (Mont Mary nappe, Italian Western Alps)

In the Austroalpine Mont Mary nappe (Italian Western Alps) discrete zones of mylonites–ultramylonites developed from coarse-grained, upper amphibolite facies metapelites of pre-Alpine age. The syn–mylonitic mineral assemblage is quartz–biotite–muscovite–plagioclase–garnet–sillimanite–ilmenite–graphite, and formed via the model hydration reaction: Grt₁+Kfs+H₂O=Bt₂+Ilm₂+Qtz+Ms± Sil .Grain-size reduction of about three orders of magnitude was accompanied by extensive recrystallization of all minerals except sillimanite, and by compositional changes of garnet and biotite. Deformation took place at temperatures of 510–580  °C under low-pressure conditions (0.25–0.45 GPa) and corresponds to the latest stages of pre-Alpine metamorphic evolution. The pre-Alpine mylonitization conditions were close to the brittle-ductile transition, as indicated by syn–mylonitic generation of pseudotachylytes and high differential stress inferred from quartz grain-size piezometry. The brittle-ductile behaviour at a relatively high temperature, and the absence of annealing textures in quartz aggregates, are suggestive of water-deficient conditions during mylonitization. These were accomplished through progressive consumption of water by syn–kinematic hydration reaction and by adsorption onto the greatly increased grain boundary area resulting from dynamic recrystallization.     

Modeling of Cs+ diffusion and retention in the DI-A2 experiment (Mont Terri). Uncertainties in sorption and diffusion parameters

In the DI-A2 experiment several non-reactive and reactive tracers were injected as a pulse in a packed-off borehole in the Opalinus Clay. Unlike the previous DI-A1 test, the design of the Teflon filter in the injection borehole forced the water to flow through the filter and the open space between the filter and the borehole wall (the filter itself did not act as a diffusion barrier between the circulating solution and the rock). The decrease in tracer concentration in the liquid phase was monitored during a period of a year. Afterwards, the borehole section was overcored and the tracer profiles in the rock were analyzed. A main interest of this experiment was to understand the chemical behavior of sorbing tracers: Cs⁺ (stable), ⁸⁵Sr²⁺, ⁶⁰Co²⁺ and Eu³⁺ (stable). The complete dataset (except for Eu³⁺ because of strong sorption to experimental equipment) was analyzed in a previous study with a 2D diffusion–reaction model and the derived diffusion and sorption parameters were compared with laboratory data. As in DI-A1, a difference by a factor of about 2 for sorption (magnitude of the Freundlich isotherm) was obtained between in situ and laboratory batch sorption experiments.Recent experimental and modeling studies have shown equivalent Cs⁺ sorption on intact and disaggregated Opalinus Clay samples. In view of these developments, new modeling of Cs⁺ diffusion and retention in the DI-A2 experiment has been performed using CrunchFlow. The calculations include transport by diffusion and a multisite cation exchange model to account for the retention of Cs⁺. The new results show that upscaling of Cs⁺ sorption from laboratory to field is no longer required. However, a difference in sorption by a factor of about 2 is still explained by the use of different versions of the same cation exchange model (a small difference in the selectivity coefficient for one type of site). This uncertainty in sorption leads to an uncertainty in the effective diffusion coefficient (D_e) for Cs⁺, also by a factor of 2 (2–4 × 10⁻¹⁰ m²/s). Clearly, the values of D_e obtained are correlated with the strength of sorption in the model, with stronger sorption leading to larger D_e values. Discrimination between the two versions of the exchange model is not possible when using only the results of the in situ test. Additionally, during early times (t < 10 days) the drop in Cs⁺ concentration in the circulation system is slower than expected. Due to the experimental setup, this slow decrease in concentration cannot be caused by the filter in the contact between borehole and rock. Poor mixing in the circulation system could explain this effect.     

Hydrogeological modeling of radionuclide transport in low permeability media: a comparison between Boom Clay and Ypresian Clay

Deep low-permeability clay layers are considered as suitable environments for disposal of high-level radioactive waste. In Belgium, the Boom Clay is the reference host formation and the Ypresian Clay an alternative host formation for research and safety and feasibility assessment of deep disposal of nuclear waste. In this study, two hydrogeological models are built to calculate the radionuclide fluxes that would migrate from a potential repository through these two clay formations. Transport parameter heterogeneity is incorporated in the models using geostatistical co-simulations of hydraulic conductivity, diffusion coefficient and diffusion accessible porosity. The calculated radionuclide fluxes in the two clay formations are compared. The results show that in the Ypresian Clay larger differences between the fluxes through the lower and the upper clay boundary occur, larger total output radionuclide amounts are calculated and a larger effect of parameter heterogeneity on the calculated fluxes is observed, compared to the Boom Clay.